Novel n-arylcarbamic acid esters

ABSTRACT

New N-arylcarbamic acid esters of the formula   wherein R4 is hydrogen or is defined as R4 is defined above, and Y and Y&#39;&#39; are oxygen or sulfur, ARE OUTSTANDINGLY EFFECTIVE IN REGULATING THE GROWTH OF PLANTS, I.E., TO INHIBIT, STIMULATE OR ALTER THE GROWTH OF PLANTS.   IN WHICH R is lower aliphatic hydrocarbyl, optionally substituted, R1, R2 and R3, which may be identical or different, are each hydrogen, alkyl, cycloalkyl, alkoxy, haloalkyl or halogen, R4 is alkyl, alkenyl, alkynyl, cycloalkenyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl or alkylthioalkyl, acylalkyl (i.e., alkanoyloxyalkyl), alkoxycarbonylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, or an optionally substituted cycloalkyl, aryl, aralkyl, aryloxyalkyl or arylthioalkyl radical, or the grouping

United States Patent [191 Metzger et al.

[ NOV. 18, 1975 NOVEL N-ARYLCARBAMIC ACID ESTERS [75] Inventors: Carl Metzger,

Wuppertal-Vohwinkel; Gerhard Jager, Wuppertal-Elberfeld; Klaus Liirssen, Koenigsdorf, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 22 Filed: June 23, 1972 21 Appl. No.: 265,909

[30] Foreign Application Priority Data June 23, 1971 Germany 2131028 Mar. 23, 1972 Germany 2214057 [52] US. Cl 260/471 C; 71/88; 71/100;

[51] Int. Cl. C07C 125/06 [58] Field of Search 260/471 C, 404, 470

[56] References Cited UNITED STATES PATENTS 3,547,977 12/1970 Richter ..260/47lC' Primary Examiner-Robert Gerstl Assistant Examiner-L. A. Thaxton Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT New N-arylcarbamic acid esters of the formula 4 7 R 42011 -1-o0oR in which R4 C- II wherein R is hydrogen or is defined as R is defined above, and

Y and Y are oxygen or sulfur,

are outstandingly effective in regulating the growth of plants, i.e., to inhibit, stimulate or alter the growth of plants.

19 Claims, N0 Drawings NOVEL N-ARYLCARBAMIC ACID ESTERS The present invention relates to certain new N-arylcarbamic acid esters, to their use as plant-growthregulating agents, and to.plant-growth-regulating compositions containing them.

It has already been disclosed that maleic acid hydrazide can be used for keeping down plant growth and for suppressing undesired side shoots in tobacco or in tomatoes. However, its inhibiting action is not always entirely satisfactory if low amounts and concentrations are used. Equally, its toleration by plants is not always good, especially at high concentrations (see US. Pat. Nos. 2,575,954; 2,614,916 and 2,805,926; British Pat. Specification No. 672,596; and W.H. Andrew and SR. Andrew, Can. 1. Biol. 31,426 (1953)).

The present invention provides, as new compounds, N-arylcarbamic acid ester compounds of the general fonnula in which 7 R is lower aliphatic hydrocarbyl by which is meant a hydrocarbon radical containing up to about 10 carbon atoms, e.g., open-chain aliphatic, which can be saturated or olefinically or acetylenically unsaturated, or cycloaliphatic, and lower aliphatic hydrocarbyl substituted with hydroxy, halogen, alkoxy, or aryl, wherein the alkoxy or aryl are also lower, i.e., contain up to about 10 carbon atoms; more specifically R is alkyl, alkenyl, alkynyl, cycloalkyl, hydroxyalkyl,

hydroxyalkenyl, hydroxyalkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl or aralkyl that may be substituted in the aryl part,

R R and R, which may be identical or different,

are each hydrogen, alkyl, cycloalkyl, alkoxy, haloalkyl or halogen,

R is alkyl, alkenyl, alkynyl, cycloalkenyl, haloalkyl,

haloalkenyl, haloalkynyl, alkoxyalkyl or alkylthioalkyl, acylalkyl (i.e., alkanoyloxyalkyl), alkoxycarbonylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, or an optionally substituted cycloalkyl, aryl, aralkyl, aryloxyalkyl or arylthioalkyl radical, or the grouping wherein R is hydrogen or is defined as R is defined above and Y and Y are oxygen or sulfur.

In formula (I) it is preferred that R should be straight-chain'or branched alkyl with one to four carbon atoms, straight-chain or branched alkenyl with three to six carbon atoms, straight-chain or branched alkynyl with three to six carbon atoms, cycloalkyl with five to eight carbon atoms, hydroxyalkyl with two to four carbon atoms, hydroxyalkenyl or hydroxyalkynyl with, in either case, three to six carbon atoms, alkoxyalkyl with one to four carbon atoms in the alkoxy part and two to four carbon atoms in the alkyl part, haloalkyl with one to four carbon atoms and one to three halogen atoms (especially fluorine and chlorine), haloalkenyl or haloalkynyl with, in either case, three to six carbon atoms and one to three halogen atoms (especially chlorine) or aralkyl with one to four carbon atoms in the alkyl part and six to ten carbon atoms in the aryl part, this aryl part optionally carrying one or more substituents, preferably selected from halogen (especially fluorine, chlorine or bromine), branched or straight-chain alkyl with one to four carbon atoms, haloalkyl with one to four carbon atoms and one to three halogen atoms, alkoxy with up to four carbon atoms and nitro;

that R, R and R, which may be alike or different, should each be hydrogen, fluorine, chlorine, bromine, straightchain or branched alkyl with one to four carbon atoms, cycloalkyl with five to seven carbon atoms, straight-chain or branched alkoxy with one to four carbon atoms, haloalkyl with one or two carbon atoms and two to five halogen atoms (especially fluorine or chlorine);

and that R should be straight-chain or branched alkyl with one to six carbon atoms or haloalkyl with one to six carbon atoms and one to three halogen atoms (especially fluorine of chlorine), straight-chain or branched alkenyl with three to six carbon atoms or haloalkenyl with three to six carbon atoms and one to four halogen atoms (especially fluorine or chlorine), straight-chain or branched alkynyl with three to six carbon atoms or haloalkynyl with three to six carbon atoms and one to four halogen atoms (especially fluorine or chlorine), alkoxyalkyl, alkylthioalkyl or acylalkyl or alkoxycarbonylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl with one to four carbon atoms in the alkoxy or alkylthio or acyl (i.e. alkanoyl) part and one to four carbon atoms in the alkyl part, optionally substituted cycloalkyl with three to eight carbon atoms in the cycloalkyl part, aryl with six to ten 10 carbon atoms, or aralkyl, aryloxyalkyl or arylthioalkyl with, in each case, six to 10 carbon atoms in the aryl part and one to three carbon atoms in the alkyl part, the aryl part of the four last-mentioned radicals optionally carrying one or more substituents selected from halogen (preferably fluorine, chlorine or bromine), straightchain or branched alkyl or alkoxy with, in either case, one to three carbon atoms and haloalkyl with one or two carbon atoms and one to five halogen atoms (especially fluorine or chlorine), or the grouping R" CY, where Y is oxygen or sulphur and R is hydrogen or is defined as R has just been defined above.

The compounds of the formula (I) have been found to possess very good plant-growth-influencing properties. Surprisingly, the N-arylcarbamic acid esters according to the invention show a considerably greater The present invention also provides a process for the preparation of an N-arylcarbamic acid ester of the formula (l) in which an N-chloromethyl-N-arylcarbamic acid ester of the general formula Cl-CH ll-C OOR in which R, R, R and R have the meanings stated above,

is reacted (a) with a compound of the general formula H-Y-R (lll) in which R and Y have the meanings stated above, in the presence of an acid-binding agent and optionally in the presence of a solvent. or (b) with a compound of /CH2-S-C H If lsopropyl-Nchloromethyl-N-( 3-chlorophenyl carbamate and sodium acetate are used as the starting materials according to process variant (b), the course of the reaction can be represented by the following equation:

As examples of the N-chloromethyl-N-aryl carbamates (II) that can be used according to the invention, there may be mentioned: Isopropyl-N-chloromethyl-N- phenyl carbamate, 2-Chloroethyl-N-chloromethyl-N- phenylcarbamate, lsopropyl-N-chloromethyl-N-( 3- chlorophenyl)-carbamate, 2-Chloroethyl-N- chloromethyl-N-(3-chlorophenyl)-earbamate, 4- Chloro-Z-butynyl-N-chloromethyl-N-(3-chloro- 4 phenyl )-carbamate, 3 -Butynyl-N-chloromethyl-N-( 3- chlorophenyl)-carbamate, Methyl-N-chloromethyl-N- (3 ,4-dichlorophenyl )-carbamate, Isopropyl-N- chloromethyl-N-(2,5-dichlorophenyl)-earbamate, 2- C hloroethyl-N-chloromethyl-N-( 2,5-dichlorophenyl carbamate, Isopropyl-N-chloromethyl-N-(2-methyl-5- chlorophenyl)-carbamate, 2-Chloroethyl-N- chloromethyl-N-(Z-methyl-5-chlorophenyl)-carbamate, Isopropyl-N-chloromethyl-N-( 2-methoxy-5- chlorophenyl )-carbamate 2-Chloroethyl-N- chloromethyl-N-(2-methoxy-5-chlorophenyl)-carbamate, Isopropyl-N-chloromethyl-N-( 3-methylphenyl)- carbamate and lsopropyl-N-chloromethyl-N-(3-trifluorome thylphenyl )-carbamate.

The N-chloromethyl-N-aryl carbamates of the formula (ll) used as starting materials have not hitherto been described in the literature, but can be prepared by a process, which does not form part of the state of the art, that comprises reacting carbamic acid esters with paraformaldehyde in the presence of thionyl chloride in an inert solvent at temperatures between +10C and +l 20C. This process is the subject of a separate patent application.

Preferably, in formula (IV), A is ammonium, dialkylammonium or trialkylammonium with one to four carbon atoms in each alkyl moiety (which may be straight-cahin or branched), a sodium ion or a potassium ion, or represents half of a magnesium ion or of a calcium ion.

As examples of the alcohols, mercaptans, phenols, thiophenols, carboxylic acids and thiocarboxylic acids (III) and their salts (IV) that can be used according to the invention, there may be mentioned: methanol, ethanol, propanol, isopropanol, tert.-butanol, allyl alcohol, propargyl alcohol, 3-methylbutynol-(3), butenol- (3); 2-chloroethanol, 4-chloro-2-butynol, cyclohexa- NaCl nol, glycol monomethyl ether, benzyl alcohol, 2,4- dichlorophenol, 4-chlorophenol, methylmercaptan, ethylmercaptan, propylmercaptan, isopropylmereaptan, allylmercaptan, benzylmereaptan, 4-chlorothiophenol, sodium formate, sodium acetate, sodium monochloroaeetate, sodium dichloroacetate, sodium 2,2-dichloropropionate, sodium phenylacetate, sodium benzoate, potassium acetate, sodium thioacetate, so-

dium butyrate, sodium valerate, sodium propionate, sodium isobutyrate, sodium trifiuoroacetate,sodium laevuleate, sodium cretonate,sodium salt of succinic acid monoester, sodium salt of maleic acid monoester and sodium salt of fumaric' acid mono ester.

The alcohols, mercaptans, phenols, thiophenols, carboxylic acids and thiocarboxylic acids as well as their salts, which correspond to the formulae (Ill) and (IV) are used as starting substances, are known. I

As a diluent in the reaction according to process variant (a) there may be used any inert organic solvent, especially a hydrocarbon, such as benzine, benzene or toluene, a halogenated hydrocarbon, suchas dichloromethane, chloroform or carbon tetrachloride, or an ether, such as diethyl ether, dioxane or tetrahydrofuran.

Any customary acid-binder can be used as the acidbinding agent, but it is preferred to use an alkali metal hydroxide, an alkali metal carbonate or atertiary organic base: sodium carbonate, triethylamine a'nd pyri- In carrying out process variant (a), lto 1.5 moles of the compound of the formula (III) and 1 to 2 moles of an acid-binding agent are preferably used per mole of N-chloromethyl N-arylcarbamic acid ester of the formula (II). A further excess over the stoichiometric amounts does not result in any significant improvement in yield.

In order to isolate the compounds of the formula (I), the hydrochloride or chloride produced is removedby filtering it and then thoroughly rinsing the reaction solution with water; the solution is dried over freshly calcined sodium sulphate and subsequently distilled. The compounds of the formula (1) are mostly water-clear liquids that can easily be distilled. In some cases, however, oils that cannot be distilled are obtained.

As a diluent for the reaction according to process variant (b), there may be used any polar organic solvent, preferably a nitrile, such as acetonitrile and tolunitrile, a sulphoxide, such as dimethylsulphoxide, or an amide, such as dimethylformamide.

The reaction temperatures for process variant (b) can be varied over a fairly wide range. In general, the reaction is carried out at from 0 C to 150 C, preferably from 20 C to 100 C.

In carrying out process variant (b), 1 mole of the compound of the formula (IV) is generally employed per mole of the compound of the formula (II).

In order to isolate the compound of the formula (I), the chloride produced is filtered off, the filtrate is evaporated to dryness and the residue is taken up in an organic solvent. After brief shaking with water, the organic phase is dried and thereafter the solvent is distilled off in vacuo. The product thus obtained is in many cases pure but can be further purified by distillation, if necessary.

The preparation of compounds of this invention and the process employed is illustrated in and by the follow ing preparative Examples.

EXAMPLE 1 Preparation of Isopropyl N-methoxymethyl-N-phenyl r carbamate v A mixture of 23.9 g (0.746 mole) of methanol and 37.8 g (0.373 mole) of triethylamine in ml of anhydrous benzene was slowly added dropwise, whilst stir- 7 EXAMPLE 2 Preparation of Isopropyl-N-propylmercaptomethyl-N-( 3-chloropheny1)-carbamate b x H SCH CI-I CH O-OCH (C11 2 A mixture of 15.2 g (0.2 mole) of n-propylmercaptan and 24.2 g (0.24 mole) of triethylamine in 160 ml of anhydrous benzene was added dropwise, whilst stirring, to a solution of 52.4 g (0.2 mole) of lsopropyl-N- chloromethyl-N-(3-chlorophenyl)-carbamate in 200 ml of anhydrous benzene at 20 C. The temperature was kept at 20 C. Thereafter, the mixture was heated for one hour under reflux. After cooling, the triethylamine hydrochloride produced was filtered off and the resulting benzene solution was washed with water and dried over freshly calcined sodium sulphate. After distilling off the solvent, an oil remained, which was distilled in vacuo. 51.9 g (86% of theory) of lsopropyl-N- propylmercaptomethyl-N-( 3-chlorophenyl )-carbamate of boiling point 158 C/l mm Hg were obtained.

EXAMPLE 3 Preparation of Methyl-N-( 2,4-dichlorophenoxymethyl )-N-( 4-chlorophenyl)-carbamate I Cl (L-OCH A solution of 16.3 g (0.1 mole) of 2,4-dichlorophenol and 14 ml (0.1 mole) of triethylamine in ml of benzene was added dropwise, over the course of 15 minutes, to a solution of 23.4 g (0.1 mole) of Methyl-N- chloromethyl-N-(4-chloropheny1)-carbamate in 200 ml of dry benzene. Thereafter the triethylamine hydrochloride was filtered off, the filtrate was washed with 5% strength sodium hydroxide solution and water, and after drying over calcined sodium sulphate the benzene was distilled off under reduced pressure. 52.4 g (92% 8 A mixture of 52.4 g (0.2 mole) of lsopropyl-N- chlor0methyl-N-( 3-chlorophenyl )-carbamate and 24.6 g (0.3 mole) of anhydrous sodium acetate in 700 ml of anhydrous acetonitrile was boiled for four hours under of theory) of Methyl-N-(2,4-dichlorophenoxymethyl)- 5 reflux. After cooling, the salts were filtered off, the fil- N-(4-chlorophenyl)-carbamate, melting at 7980 C trat e wasevaporated, the residue was dissolved in 300 after recrystallization from ethanol, were obtained. ml of ether and the ether solution was washed with EXAMPLE 4 water and dried over freshly calcined sodium sulfate. 0 Thereafter, the solvent was distilled off and the result- Preparation of ing oil was distilled in vacuo. 34.2 g (95% of theory) of lsopropyl-N-acetoxymethyl-N-( 3-chlorophenyl )'-car- Isopropyl-N-acetoxymethyl-N-( 3-chlorophenyl )carbabamate mate of boiling point 134 C/0.3 mm Hg and refractive index 12,, 1.5074 were obtained. H O-COCI-i 2 3 H The following compounds may be prepared by meth- OO CPKCH ods analogous to those given in the foregoing Exam- 3 2 ples.

Melting Point. C Compound 7 Boiling point. C/mm Hg No. R R R" R Y R Compound Name Refractive index n,,'-'

l CH H H H O CH; Methyl-N-methoxymethyl-N- 8687/0.3

phenyl carhamate 2 CH,-, H H H O (2H5 Meth l-N-ethoxymethyl-N- l()4/0.35

phenyl carhamate 3 CH;, H H H O (CH;, ):CH MethyLN-isopropoxymethyl- 79-8 1 /O. l 5

N-phenyl carbamate 4 CH3 H H H 0 (3H, MethyLN-n-hutox3.'methyl-N- 93-94/().l5

, phenyl carhamate 5 (CH;,)2CH H H H O CH; lsopropyl-N-methoxymethyl- 98/0.4

N-phenyl carbamate (1 (CHKECH H H H O (2H5 lsopropyl-N-ethoxyethyl-N- 92/03 v phenyl carbamate 7 (CHHMCH H H H O 'CHH; lsopropyl-N-n-propoxymethyll28l3()/0.8

1 N-phenyl carbamute 8 (CH;.)' 'CH H H H O (CH:) -CH lsopropyLN-isopropoxymeth- 94/02 yl-N-phenyl carbamate 9 (CHQZCH 3-Cl H H 0 CH1 lsopropyl-N-methoxymethyL 1 10/01 NJ-chloroghenvl carhamate (Compounds H; to 43 hercinbelo haw not been named for the sake of brevity. inasmuch as the nomenclature is analogous to that given above.)

Compound Melting point. C Boiling point. "C/mm Hg '1 a o 1 e 4- (continued) Melting point, c Compound Boiling point, C/mzn Hg NO. R R R R Y R Refractive Index 11 124 (029 05 a a a CtI -(CH 35-57 125 (CE...) c5 H H H 0 til-@ 1-5414 12s (CH CH H n H 0 99 100 The active compounds according to the invention interfere with the physiological phenomena of plant growth and can therefore be used as plant growth regulators.

The different effects of the active compounds essentially depend on the point in time at which they are used, relative to the stage of development of the seed or of the plant, and on the concentrations employed.

Plant-growth regulators are used for various purposes that are related to the state of development of the plant.

Thus, the seed dormancy can be broken by means of plantgrowth regulators in order to cause the seeds to germinate at a certain time that is desired, but at which the seed itself displays no readiness to germinate. Seed germination itself can be either inhibited or promoted by such active compounds depending on the concentration employed. This inhibition or promotion refers to the development of the seedling the bud dormancy of plants, that is to say the endogenic annual cycle, can be influenced by the active compounds, so that the plants, for example, shoot or blossom at a point in time at which they normally show no readiness to shoot or blossom.

It is also possible to delay the opening of buds, for example in order to prevent frost damagein areas subject to frost.

The shoot growth or root growth can be promoted or inhibited by the active compounds, depending on the concentration. Thus,-it is possible, forexample, very greatly to inhibit the growth of the fully formed plant or converselyto bring the plant altogether to a more robust habitus, or to bring about stunted growth.

The inhibition of growth at the edges of roads and paths is of economic interest. Furthermore, the frequency of cutting the grass (mowing) of lawns can be reduced. Equally, the growth of woodlands can be inhibited.

During the growth of the plant, the lateral branching can also be increased by chemically breaking the apical dominance. Interest in this exists, for example, in the propagation of plants by cuttings. Depending on the concentration, it is however also possible. to inhibit the growth of side shoots, for example in order to prevent the formation of side shoots in tobacco plants after decapitation and thereby promote leaf growth.

Growth regulators can also be used to reduce the transpiration rate of plants in order to prevent damage through drying out.

In the case of influencing blossom formation, either a retardation of blossom formation or an acceleration of blossom formation can be achieved depending on the concentration and on the point in time at which the substance is used. Under certain circumstances it is also possible to increase the setting of blossoms, and these effects arise if the appropriate treatments are carried out at the time of normal blossom formation. Furthermore, the formation of predominantly female or predominantly male blossoms can be achieved.

Fruit-setting can be promoted, so that more fruit or seedless fruit is formed (parthenocarpy). Under certain conditions, the premature fall of fruit can also be pre- -vented, or the fall of fruit can, to a certain degree, be

promoted in the sense of a chemical thinning-out. The promotion of the fall of fruit can, however, also be utilized by carrying out the treatment at harvest time, whereby harvesting is facilitated.

Increases in yield by means of growth regulators can be achieved both by promoting the setting of fruit and by the formation of larger fruit or by promotion of vegetative growth. Furthermore, it is possible to stimulate the synthesis or secretion of secondary vegetable constituents (for example the latex secretion of rubber trees).

Some of the active compounds accordinig to the invention show herbicidal properties at higher concentrations. Eurthermore, the active compounds according to the invention possess insecticidal, acaricidal and, in some cases, fungitoxic activity.

The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and- /or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents (see Agricultural Chemicals, March 1960, pages 35 to 38).

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane orxparaffins, for example mineral oil fractions, alcohols,.such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile,

as well as water. F

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite of diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina-or silicates.

Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other active substances. i

The formulations, in general, contain from 0.1 to 95,. preferably from 0.5 to 90, per cent by weight of active compound.

The active compounds can be used as such, in the form of their formulations or in the fonn of the application forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They may be employed in any customary manner, for example by watering, spraying, atomising, sprinkling or dusting.

The amount of active substance employed can vary over a fairly wide range; it depends essentially on the nature of the desired effect. In general, however, the amounts used are from 0.1 to 25 kg/hectare, preferably from 0.5 to 20 kg/hectare.

The present invention also provides a plant-growthregulating composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of regulating the growth of plants which comprises applying to the plants or a-plant habitat a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The plant-growth-regulating activity of the compounds of the present invention is illustrated in and by the following test Examples.

EXAMPLE A Growth inhibition in grass Solvent: 10 parts by 'weight of methanol Emulsifier: 2 parts by weight of polyethylene-Serbitan monolaurate.

, In order to prepare a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with the indicated amounts of solvent and emulsifier and made up to the desired concentration with water.

Grass plants 3 to 4 cm high were sprayed with the active-compound preparations until dripping wet. After 14 days, the additional growth was measured and the inhibition of growth in per cent of the additional growth of the control plants was-calculated. The damage was classified on a scale from O to 5, with 0 denoting no damage and 5 denoting the death of the plants. a

The active compounds, active-compound concentrations and results can be seen from Table A below:

Inhibition of growth in grass (Festuca pratensis) Irihibition/ Active compound Concentration damage (pp 0 w A 2000 '70 =7 9 m rr r' I o l 1000 ,u L 500. 557 /1 (known) 2000 v 5 H( 1000 5 c 5 30 1 4 (kn own I z' z, pmmd 9) 2000 w 100 1 Q c00-ca(c1a 1000 100 -5 1 c 500 40 r 1 21 EXAMPLE B Inhibition of growth in cress seedlings which the active-compound preparation had been dripped. Since the cress seeds adhere to moist filter paper, the latter was placed vertically in a beaker of 250 ml capacity. The beaker was filled with ml of activecompound preparation and was covered with a glass I plate. After 4 days the seedlings were measured and the percentage inhibition of elongation growth was calculated. relative to the control (distilled water with the appropriate amounts of solvent and emulsifier).

The active compounds, active-compound concentrations and results are shown in Table B below:

Table B Inhibition of growth in cross seedlinrrs Inhibition Active compound Concentration (pp NH I lkrH 200 (known) coo-cH(c 4 (known) an -o-cn ll: 2 200 7 coo -cu(c1i v CH2-O-CH2-C5CH 200- 0 d coo-011mg) v 7 C1 (Couipound 1 (CH2 O C(CH3)3 200 0 7 coo-cutesy 5 (:1 7 (Compound 16 9 5 cH -O-C-C CH coo-cu(ca C1 (Compound o-cocH d \COO-CH(CH3)2 cl (Example 4) T a b 1 e B (continued) Active compound Conccn- Inhibition tration (pp CH -O-CO-CH CJ.

a \COO CH(CH3)2 200 80 a C1 (Compound 57 N Cl-l -O--CO-CHCl I coo-cH(CH c1 (Compound 5 It will be understood that the specification and exam wherein ples are illustrative but not limitative of the present in- R" is hydrogen, alkyl of from one to 17 carbon vention and that other embodiments within the spirit atoms; alkenyl of from three to carbon atoms; and scope of the invention will suggest themselves to alkynyl of from three to six carbon atoms; chloroalthose skilled in the art. kyl of from one to six carbon atoms and one to What is claimed is: three chlorine atoms; chloroalkenyl of from three 1. N-arylcarbamate of the formula: to six carbon atoms and one to four chlorine atoms; chloroalkynyl of from three to six carbon atoms and one to four chlorine atoms; or alkoxyalkyl, al- 4 3 kylthioalkyl methylcarbonylalkyl, methoxycarbo- R Y CH2 N C00}: 0 nylalkyl of from one to four carbon atoms per alkyl R moiety; cycloalkyl of from three to eight carbon 3 atoms, cycloalkenyl of from five to six carbon atoms; aryl, aralkyl, or aroxyalkyl of from six to 10 carbon atoms in the aryl moiety and one to four carbon atoms in the alkyl moiety, wherein said aryl wherein moiety may carry at least one of fluorine, chlorine R is alkyl of from one to four carbon atoms; and bromine, alkyl or alkoxy of from one to four alkenyl of from three to six carbon atoms; alkynyl of Carbon atoms and chloroalkyl of from one Or two from three to six carbon atoms; cycloalkyl of from O toms an One to five Chlorine atoms, and five to eight carbon atoms; hydroxyalkyl of fr m wherein the alkyl moiety of said aralkyl may be two to four carbon atoms; hydroxyalkenyl or hy- I Substituted with Chlorine and droxyalkynyl of from three to six carbon atoms; .Y and Y are oxygen. alkoxyalkyl of from one to four carbon atoms in the 2. Compound as claimed in claim 1 wherein R is alkyl alkoxy moiety and two to four carbon atoms in the of about four carbon atoms. alkyl y; ChlOrO alkyl of from One to fOUr 3. Compound as claimed in claim 1 wherein R is alkeatoms and one to three Chlorine atoms; chlonyl or alkynyl of from three to six carbon atoms. roalkenyl OI' chloroalkynyl Cf from three to six car- 4. Compound as laimed in laim 1 wherein R is ybOll atoms and one IO three chlorine atoms; 01' aralv cIoalkyl of from five to eight carbon atoms kyl of from one to four carbon atoms in the alkyl 5 C d as l i d i l i 1 h i R i h moiety and Six to 10 Carbon atoms in the y droxyalkyl of from two to four carbon atoms, hydroxy wherein the y moiety y carry at least one yalkenyl or hydroxyalkynyl of from three up to six carof fluorine, chlorine, and bromine, alkyl of from 'b atoms one to four carbon atoms, chloroalkyl of from one 6. Compound as claimed in Claim 1 wherein R i l to four carbon atoms and one to three chlorin? oxyalkyl of up to four carbon atoms in each alkyl moiatoms, alkoxy of from up to 4 carbon atoms and m- 3 7. compound as claimed in claim 1 wherein R is chlo- R R- and mdwlduany selecited from roalhyl chloroalkenyl and chloroalkynyl of up to six conslstmg of hydrogen fiuorme Chlormei carbon atoms and from one to three halogen atoms. bromine, alkyl of from one to four carbon atoms, 8. Compound as Claimed in claim 1 wherein R is aral cycloalkyl of from five to Seven carbon atoms kyl of from one to four carbon atoms in the alkyl moioxy of from one to four carbon atoms, chloroalkyl ety and Six to 10 carbon atoms in the aryl moiety, of q one two Carbon atoms and two to five wherein the aryl moiety may be substituted with at least fi m one member selected from the group consisting of R 15 the grouping halogen, alkyl of from one to four carbon atoms, haloalkyl of from one to four carbon atoms and one to three halogen atoms, alkoxy of from one to four carbon atoms and nitro.

9. Compound as claimed in claim 1 wherein R, R and R are individually selected from the group consisting of hydrogen, fluorine, chlorine, bromine, alkyl with one to four carbon atoms, cycloalkyl with five to seven carbon atoms, straightchain or branched alkoxy with one to four carbon atoms or chloroalkyl with one or two carbon atoms and two to five chlorine atoms.

10. Compound as claimed in claim 1 designated Methyl-N-methoxymethyl-N-phenyl carbamate.

11. Compound as claimed in claim 1 designated Methyl-N-ethoxymethyl-N-phenyl carbamate.

12. Compound as claimed in claim 1 designated Methyl-N-isopropoxymethyl-N-phenyl carbamate.

13. Compound as claimed in claim 1 designated Methyl-N-n-butoxymethyl-N-phenyl carbamate.

14. Compound as claimed in claim 1 designated lsopropyl-N-methoxymethyl-N-phenyl carbamate.

15. Compound as claimed in claim 1 designated Iso- 5 propyl-N-ethoxymethyl-N-phenyl carbamate. 

1. N-ARYLCARBAMATE OF THE FORMULA:
 2. Compound as claimed in claim 1 wherein R is alkyl of about four carbon atoms.
 3. Compound as claimed in claim 1 wherein R is alkenyl or alkynyl of from three to six carbon atoms.
 4. Compound as claimed in claim 1 wherein R is cycloalkyl of from five to eight ring carbon atoms.
 5. Compound as claimed in claim 1 wherein R is hydroxyalkyl of from two to four carbon atoms, hydroxyalkenyl or hydroxyalkynyl of from three up to six carbon atoms.
 6. compound as claimed in claim 1 wherein R is alkoxyalkyl of up to four carbon atoms in each alkyl moiety.
 7. compound as claimed in claim 1 wherein R is chloroalhyl chloroalkenyl and chloroalkynyl of up to six carbon atoms and from one to three halogen atoms.
 8. compound as claimed in claim 1 wherein R is aralkyl of from one to four carbon atoms in the alkyl moiety and six to 10 carbon atoms in the aryl moiety, wherein the aryl moiety may be substituted with at least one member selected from the group consisting of halogen, alkyl of from one to four carbon atoms, haloalkyl of from one to four carbon atoms and one to three halogen atoms, alkoxy of from one to four carbon atoms and nitro.
 9. Compound as claimed in claim 1 wherein R1, R2 and R3 are individually selected from the group consisting of hydrogen, fluorine, chlorine, bromine, alkyl with one to four carbon atoms, cycloalkyl with five to seven carbon atoms, straightchain or branched alkoxy with one to four carbon atoms or chloroalkyl with one or two carbon atoms and two to five chlorine atoms.
 10. Compound as claimed in claim 1 designated Methyl-N-methoxymethyl-N-phenyl carbamate.
 11. Compound as claimed in claim 1 designated Methyl-N-ethoxymethyl-N-phenyl carbamate.
 12. Compound as claimed in claim 1 designated Methyl-N-isopropoxymethyl-N-phenyl carbamate.
 13. Compound as claimed in claim 1 designated Methyl-N-n-butoxymethyl-N-phenyl carbamate.
 14. Compound as claimed in claim 1 designated Isopropyl-N-methoxymethyl-N-phenyl carbamate.
 15. Compound as claimed in claim 1 designated Isopropyl-N-ethoxymethyl-N-phenyl carbamate.
 16. Compound as claimed in claim 1 designated Isopropyl-N-n-propoxymethyl-N-phenyl carbamate.
 17. Compound as claimed in claim 1 designated Isopropyl-chloroacetoxymethyl-N-phenyl carbamate.
 18. Compound as claimed in claim 1 designated Isopropyl-N-acetoxymethyl-N-3-chlorophenyl carbamate.
 19. Compound as claimed in claim 1, designated isopropyl-N-n-propanoyl-oxymethyl-N-(3-chlorophenyl)-carbamate. 